Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors

ABSTRACT

Catalyst compositions useful for the polymerization of olefins are disclosed. These compositions comprise a Group 8-10 metal complex comprising a bidentate or variable denticity ligand comprising one or two nitrogen donor atom or atoms independently substituted by an aromatic or heteroaromatic ring(s), wherein the ortho positions of said ring(s) are substituted by aryl or heteroaryl groups. Also disclosed are processes for the polymerization of olefins using the catalyst compositions.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of Provisional Application No.60/231,920, filed on Sep. 11, 2000, under 35 USC §119; the entirecontent of which is hereby incorporated by reference.

This application is also a continuation-in-part of application Ser. Nos.09/507,492, filed on Feb. 18, 2000, and 09/563,812, filed on May 3,2000; the entire content of both applications is hereby incorporated byreference.

FIELD OF THE INVENTION

The present invention generally relates to catalyst compositions usefulfor the polymerization or oligomerization of olefins, and to processesusing the catalyst compositions. Certain of these catalyst compositionscomprise a Group 8-10 metal complex comprising a bidentate or variabledenticity ligand comprising one or two nitrogen donor atom or atomsindependently substituted by an aromatic or heteroaromatic ring(s),wherein the ortho positions of said ring(s) are substituted by aryl orheteroaryl groups.

BACKGROUND OF THE INVENTION

Olefin polymers are used in a wide variety of products, from sheathingfor wire and cable to film. Olefin polymers are used, for instance, ininjection or compression molding applications, in extruded films orsheeting, as extrusion coatings on paper, for example photographic paperand digital recording paper, and the like. Improvements in catalystshave made it possible to better control polymerization processes and,thus, influence the properties of the bulk material. Increasingly,efforts are being made to tune the physical properties of plastics forlightness, strength, resistance to corrosion, permeability, opticalproperties, and the like, for particular uses. Chain length, polymerbranching and functionality have a significant impact on the physicalproperties of the polymer. Accordingly, novel catalysts are constantlybeing sought in attempts to obtain a catalytic process for polymerizingolefins which permits more efficient and better-controlledpolymerization of olefins.

The use of late transition metal complexes as catalysts for olefinpolymerization has recently been reviewed by Ittel et al. (Chem. Rev.2000, 100, 1169). Notwithstanding the many advances described therein,there remains a need for new late transition metal catalysts andprocesses with improved productivities under the elevated temperaturesand pressures of commercial reactor operating conditions. New catalystsand processes for these purposes are described herein.

SUMMARY OF THE INVENTION

In a first aspect, this invention relates to a catalyst compositionuseful for the polymerization of olefins, which comprises a Group 8-10metal complex comprising a bidentate or variable denticity ligandcomprising two nitrogen donor atoms independently substituted byaromatic or heteroaromatic rings, wherein the ortho positions of therings are substituted by aryl or heteroaryl groups.

In a second aspect, this invention relates to a catalyst compositioncomprising either (i) a compound of formula ee1, (ii) the reactionproduct of a metal comples of formula ff1 and a second compound Y¹, or(iii) the reaction product of Ni(1,5-cycloocatadiene)₂, B(C₆F₅)₃, aligand selected from Set 18, and optionally an olefin;

wherein:

L² is selected from Set 18;

T is H, hydrocarbyl, substituted hydrocarbyl, or other group capable ofinserting an olefin;

L is an olefin or a neutral donor group capable of being displaced by anolefin; in addition, T and L may be taken together to form a π-allyl orπ-benzyl group;

X⁻ is BF₄ ⁻, B(C₆F₅)₄ ⁻, BPh₄ ⁻, or another weakly coordinating anion;

Q and W¹ are each independently fluoro, chloro, bromo or iodo,hydrocarbyl, substituted hydrocarbyl, heteroatom attached hydrocarbyl,heteroatom attached substituted hydrocarbyl, or collectively sulfate, ormay be taken together to form a π-allyl, π-benzyl, or acac group, inwhich case a weakly coordinating counteranion X⁻ is also present;

Y¹ is either (i) a metal hydrocarbyl capable of abstracting acac fromff1 in exchange for alkyl or another group capable of inserting anolefin, (ii) a neutral Lewis acid capable of abstracting Q or W¹ fromff1 to form a weakly coordinating anion, a cationic Lewis acid whosecounterion is a weakly coordinating anion, or a Bronsted acid whoseconjugate base is a weakly coordinating anion, or (iii) a Lewis acidcapable of reacting with a π-allyl or it-benzyl group, or a substituentthereon, in ff1 to initiate olefin polymerization;

R^(3a,b) are each independently H, alkyl, hydrocarbyl, substitutedhydrocarbyl, 2,4,6-triphenylphenyl, heteroatom connected hydrocarbyl,heteroatom connected substituted hydrocarbyl, or fluoroalkyl; and

Ar^(1a-d) are each independently phenyl, 4-alkylphenyl,4-tert-butylphenyl, 4-trifluoromethylphenyl, 4-hydroxyphenyl,4-(heteroatom attached hydrocarbyl)-phenyl, 4-(heteroatom attachedsubstituted hydrocarbyl)-phenyl, or 1-naphthyl.

In a first preferred embodiment of this second aspect, the metal complexof formula ff1 is selected from Set 19;

wherein:

R^(3a,b) are each independently H, methyl, phenyl, 4-methoxyphenyl, or4-tert-butylphenyl;

Ar^(1a-d) are each independently phenyl, 4-methylphenyl,4-tert-butylphenyl, 4-trifluoromethylphenyl, 1-naphthyl, 2-naphthyl, or4-phenylphenyl; and

X⁻ is BF₄ ⁻, B(C₆F₅)₄ ⁻, BPh₄ ⁻, or another weakly coordinating anion.

In a second preferred embodiment of this second aspect, the substituentsAr^(1a-d) are 4-tert-butylphenyl or 1-naphthyl. In a third, especiallypreferred, embodiment, the catalyst composition further comprises asolid support.

In a third aspect, this invention relates to a process for thepolymerization of olefins, comprising contacting one or more olefinswith the catalyst composition of the second aspect. In a preferredembodiment, of this second aspect, the second compound Y¹ istrimethylaluminum, and the metal complex is contacted with thetrimethylaluminum in a gas phase olefin polymerization reactor.

In a fourth aspect, this invention relates to a compound of formula ii1;

wherein:

R^(3a,b) are each independently H, methyl, phenyl, 4-methoxyphenyl, or4-tert-butylphenyl; and

Ar^(1a-d) are each independently phenyl, 4-methylphenyl,4-tert-butylphenyl, 4-trifluoromethylphenyl, 1-naphthyl, 2-naphthyl, or4-phenylphenyl. Compounds of this formula are useful as ligands inconstituting the catalysts of the present invention.

In a fifth aspect, the invention relates to a process for thepolymerization of olefins, comprising contacting one or more olefinswith a catalyst composition comprising a Group 8-10 transition metalcomplex which comprises a ligand selected from Set 20;

wherein:

R^(2x,y) are each independently H, hydrocarbyl, substituted hydrocarbyl,heteroatom connected hydrocarbyl, or heteroatom connected substitutedhydrocarbyl; in addition, R^(2x) and R^(2y) may be linked by a bridginggroup;

R^(3a-f) are each independently H, alkyl, hydrocarbyl, substitutedhydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connectedsubstituted hydrocarbyl, or fluoroalkyl; and

Ar^(1a-d) are each independently phenyl, 4-alkylphenyl,4-tert-butylphenyl, 4-trifluoromethylphenyl, 4-hydroxyphenyl,4-(heteroatom attached hydrocarbyl)-phenyl, 4-(heteroatom attachedsubstituted hydrocarbyl)-phenyl, 1-naphthyl, 2-naphthyl, 9-anthracenyl,or aryl.

In a sixth aspect, this invention relates to a compound selected fromSet 21;

wherein:

R^(2x,y) are each independently H, hydrocarbyl, substituted hydrocarbyl,heteroatom connected hydrocarbyl, or heteroatom connected substitutedhydrocarbyl; in addition, R^(2x) and R^(2y) may be linked by a bridginggroup;

R^(3a-f) are each independently H, alkyl, hydrocarbyl, substitutedhydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connectedsubstituted hydrocarbyl, or fluoroalkyl; and

Ar^(1a-d) are each independently phenyl, 4-alkylphenyl,4-tert-butylphenyl, 4-trifluoromethylphenyl, 4-hydroxyphenyl,4-(heteroatom attached hydrocarbyl)-phenyl, 4-(heteroatom attachedsubstituted hydrocarbyl)-phenyl, 1-naphthyl, 2-naphthyl, 9-anthracenyl,or aryl. These compounds are are useful as ligands in constituting thecatalysts of the present invention.

In a seventh aspect, this invention relates to a catalyst compositionuseful for the polymerization of olefins, which comprises a Group 8-10transition metal complex comprising a N,N-donor ligand of the formulakk1 or kk2;

wherein:

Ar^(2a,b) are each independently aromatic or heteroaromatic groupswherein the ortho positions are substituted by aryl or heteroarylgroups;

M¹ is a metal selected from Groups 3, 4, 5, 6, 13, or 14, or is Cu, P orAs; and

L_(n) are ancillary ligands or groups which satisfy the valency of M¹,such that M¹ is either a neutral, monoanionic or cationic metal center,or is a neutral or cationic P or As, with suitable counterions such thatsaid catalyst composition has no net charge. M¹L_(n) may also be anactive site for olefin polymerization. The compounds of formula kk2 arecapable of ligating to two Group 8-10 metal centers, which may be thesame or different, where one or both of said Group 8-10 metal centersmay be active sites for olefin polymerization.

In an eighth aspect, this invention relates to a process for thepolymerization of olefins, comprising contacting one or more olefinswith the catalyst composition the seventh aspect.

We have surprisingly found that the catalyst compositions of the presentinvention can provide improved stability in the presence of an amount ofhydrogen effective to achieve chain transfer, a total productivitygreater than about 28,000 kg polyethylene per mole of catalyst at anoperating temperature of at least 60° C. (preferably greater than 56,000kg PE/mol catalyst), and/or a higher productivity in the presence of anamount of hydrogen effective to achieve chain transfer, relative to theproductivity observed in the absence of hydrogen.

DETAILED DESCRIPTION OF THE INVENTION

In this disclosure, symbols ordinarily used to denote elements in thePeriodic Table and commonly abbreviated groups, take their ordinarymeaning, unless otherwise specified. Thus, N, O, S, P, and Si stand fornitrogen, oxygen, sulfur, phosphorus, and silicon, respectively, whileMe, Et, Pr, ^(i)Pr, Bu, ^(t)Bu and Ph stand for methyl, ethyl, propyl,iso-propyl, butyl, tert-butyl and phenyl, respectively.

A “hydrocarbyl” group means a monovalent or divalent, linear, branchedor cyclic group which contains only carbon and hydrogen atoms. Examplesof monovalent hydrocarbyls include the following: C₁-C₂₀ alkyl; C₁-C₂₀alkyl substituted with one or more groups selected from C₁-C₂₀ alkyl,C₃-C₈ cycloalkyl, and aryl; C₃-C₈ cycloalkyl; C₃-C₈ cycloalkylsubstituted with one or more groups selected from C₁-C₂₀ alkyl, C₃-C₈cycloalkyl, and aryl; C₆-C₁₄ aryl; and C₆-C₁₄ aryl substituted with oneor more groups selected from C₁-C₂₀ alkyl, C₃-C₈ cycloalkyl, and aryl.Examples of divalent (bridging) hydrocarbyls include: —CH₂—, —CH₂CH₂—,—CH₂CH₂CH₂—, and 1,2-phenylene.

The term “aryl” refers to an aromatic carbocyclic monoradical, which maybe substituted or unsubstituted, wherein the substituents are halo,hydrocarbyl, substituted hydrocarbyl, heteroatom attached hydrocarbyl,heteroatom attached substituted hydrocarbyl, nitro, cyano, fluoroalkyl,sulfonyl, and the like. Examples include: phenyl, naphthyl, anthracenyl,phenanthracenyl, 2,6-diphenylphenyl, 3,5-dimethylphenyl, 4-nitrophenyl,3-nitrophenyl, 4-methoxyphenyl, 4-dimethylaminophenyl, and the like.

A “heterocyclic ring” refers to a carbocyclic ring wherein one or moreof the carbon atoms has been replaced by an atom selected from the groupconsisting of O, N, S, P, Se, As, Si, B, and the like.

A “heteroaromatic ring” refers to an aromatic heterocycle; examplesinclude pyrrole, furan, thiophene, indene, imidazole, oxazole,isoxazole, carbazole, thiazole, pyrimidine, pyridine, pyridazine,pyrazine, benzothiophene, and the like.

A “heteroaryl” refers to a heterocyclic monoradical which is aromatic;examples include 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, furyl, thienyl,indenyl, imidazolyl, oxazolyl, isoxazolyl, carbazolyl, thiazolyl,pyrimidinyl, pyridyl, pyridazinyl, pyrazinyl, benzothienyl, and thelike, and substituted derivatives thereof.

A “silyl” group refers to a SiR₃ group wherein Si is silicon and R ishydrocarbyl or substituted hydrocarbyl or silyl, as in Si(SiR₃)₃.

A “boryl” group refers to a BR₂ or B(OR)₂ group, wherein R ishydrocarbyl or substituted hydrocarbyl.

A “heteroatom” refers to an atom other than carbon or hydrogen.Preferred heteroatoms include oxygen, nitrogen, phosphorus, sulfur,selenium, arsenic, chlorine, bromine, silicon, and fluorine.

A “substituted hydrocarbyl” refers to a monovalent, divalent, ortrivalent hydrocarbyl substituted with one or more heteroatoms. Examplesof monovalent substituted hydrocarbyls include:2,6-dimethyl-4-methoxyphenyl, 2,6-diisopropyl-4-methoxyphenyl,4-cyano-2,6-dimethylphenyl, 2,6-dimethyl-4-nitrophenyl,2,6-difluorophenyl, 2,6-dibromophenyl, 2,6-dichlorophenyl,4-methoxycarbonyl-2,6-dimethylphenyl, 2-tert-butyl-6-chlorophenyl,2,6-dimethyl-4-phenylsulfonylphenyl,2,6-dimethyl-4-trifluoromethylphenyl,2,6-dimethyl-4-trimethylammoniumphenyl (associated with a weaklycoordinated anion), 2,6-dimethyl-4-hydroxyphenyl, 9-hydroxyanthr-10-yl,2-chloronapth-1-yl, 4-methoxyphenyl, 4-nitrophenyl, 9-nitroanthr-10-yl,—CH₂OCH₃, cyano, trifluoromethyl, and fluoroalkyl. Examples of divalent(bridging) substituted hydrocarbyls include: 4-methoxy-1,2-phenylene,1-methoxymethyl-1,2-ethanediyl, 1,2-bis(benzyloxymethyl)-1,2-ethanediyl,and 1-(4-methoxyphenyl)-1,2-ethanediyl. Examples of trivalenthydrocarbyls include methine and phenyl-substituted methane.

A “heteroatom connected hydrocarbyl” refers to a group of the typeE¹⁰(hydrocarbyl), E²⁰H(hydrocarbyl), or E²⁰(hydrocarbyl)₂, where E¹⁰ isan atom selected from Group 16 and E²⁰ is an atom selected from Group15.

A “heteroatom connected substituted hydrocarbyl” refers to a group ofthe type E¹⁰(substituted hydrocarbyl), E²⁰H(substituted hydrocarbyl), orE²⁰(substituted hydrocarbyl)₂, where E¹⁰ is an atom selected from Group16 and E²⁰ is an atom selected from Group 15.

The term “fluoroalkyl” as used herein refers to a C₁-C₂₀ alkyl groupsubstituted by one or more fluorine atoms.

An “olefin” refers to a compound of the formula R^(1a)CH═CHR^(1b), whereR^(1a) and R^(1b) may independently be H, hydrocarbyl, substitutedhydrocarbyl, fluoroalkyl, silyl, O(hydrocarbyl), or O(substitutedhydrocarbyl), and where R^(1a) and R^(1b) may be connected to form acyclic olefin, provided that in all cases, the substituents R^(1a) andR^(1b) are compatible with the catalyst. In the case of most Group 4-7catalysts, this will generally mean that the olefin should not containgood Lewis base donors, since this will tend to severely inhibitcatalysis. Preferred olefins for such catalysts include ethylene,propylene, butene, hexene, octene, cyclopentene, norbornene, andstyrene.

In the case of the Group 8-10 catalysts, Lewis basic substituents on theolefin will tend to reduce the rate of catalysis in most cases; however,useful rates of homopolymerization or copolymerization can nonethelessbe achieved with some of those olefins. Preferred olefins for suchcatalysts include ethylene, propylene, butene, hexene, octene, andfluoroalkyl substituted olefins, but may also include, in the case ofpalladium and some of the more functional group tolerant nickelcatalysts, norbornene, substituted norbornenes (e.g., norbornenessubstituted at the 5-position with halide, siloxy, silane, halo carbon,ester, acetyl, alcohol, or amino groups), cyclopentene, ethylundecenoate, acrylates, vinyl ethylene carbonate,4-vinyl-2,2-dimethyl-1,3-dioxolane, and vinyl acetate.

In some cases, the Group 8-10 catalysts can be inhibited by olefinswhich contain additional olefinic or acetylenic functionality. This isespecially likely if the catalyst is prone to “chain-running” whereinthe catalyst can migrate up and down the polymer chain betweeninsertions, since this can lead to the formation of relativelyunreactive π-allylic intermediates when the olefin monomer containsadditional unsaturation. Such effects are best determined on acase-by-case basis, but may be predicted to some extent throughknowledge of how much branching is observed with a given catalyst inethylene homopolymerizations; those catalysts which tend to giverelatively high levels of branching with ethylene will tend to exhibitlower rates when short chain diene co-monomers are used under the sameconditions. Longer chain dienes tend to be less inhibitory than shorterchain dienes, when other factors are kept constant, since the catalysthas farther to migrate to form the π-allyl, and another insertion mayintervene first.

Similar considerations apply to unsaturated esters which are capable ofinserting and chain-running to form relatively stable intramolecularchelate structures wherein the Lewis basic ester functionality occupiesa coordination site on the catalyst. In such cases, short chainunsaturated esters, such as methyl acrylate, tend to be more inhibitorythan long chain esters, such as ethyl undecenoate, if all other factorsare kept constant.

A “π-allyl” group refers to a monoanionic group with three sp² carbonatoms bound to a metal center in a η³-fashion. Any of the three sp²carbon atoms may be substituted with a hydrocarbyl, substitutedhydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connectedsubstituted hydrocarbyl, or O-silyl group. Examples of π-allyl groupsinclude:

The term π-benzyl group denotes an π-allyl group where two of the sp²carbon atoms are part of an aromatic ring. Examples of π-benzyl groupsinclude:

A “bridging group” refers to an atom or group which links two or moregroups, which has an appropriate valency to satisfy its requirements asa bridging group, and which is compatible with the desired catalysis.Suitable examples include divalent or trivalent hydrocarbyl, substitutedhydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connectedsubstituted hydrocarbyl, substituted silicon(IV), boron(III), N(III),P(III), and P(V), —C(O)—, —SO₂—, —C(S)—, —B(OMe)—, —C(O)C(O)—, O, S, andSe. In some cases, the groups which are said to be “linked by a bridginggroup” are directly bonded to one another, in which case the term“bridging group” is meant to refer to that bond. By “compatible with thedesired catalysis,” we mean a bridging group or substituent which eitherdoes not interfere with the desired catalysis, or acts to usefullymodify the catalyst activity or selectivity.

The term “weakly coordinating anion” is well known in the art per se andgenerally refers to a large bulky anion capable of delocalization of thenegative charge of the anion. Weakly coordinating anions, not all ofwhich would be considered bulky, include, but are not limited to:B(C₆F₅)₄ ⁻, PF₆ ⁻, BF₄ ⁻, SbF₆ ⁻, (F₃CSO₂)₂N⁻, (F₃CSO₂)₃C⁻, (Ph)₄B⁻wherein Ph=phenyl, and Ar₄B⁻ whereinAr₄B⁻=tetrakis[3,5-bis(trifluoromethyl)phenyl]-borate. The weaklycoordinating nature of such anions is known and described in theliterature (S. Strauss et al., Chem. Rev., 1993, 93, 927).

The term “ortho” is used herein in the context of the ligands of thepresent invention to denote the positions which are adjacent to thepoint of attachment of the aromatic or heteroaromatic ring to theligated nitrogen(s). In the case of a 1-attached, 6-membered ring, wemean the 2- and 6-positions. In the case of a 1-attached, 5-memberedring, we mean the 2- and 5-positions. In the case of 1-attached, fusedring aromatic or heteroaromatic rings, we mean the first positions whichcan be substituted; for example, in the case of 1-naphthyl, these wouldbe the 2- and 8-positions; in the case of 9-anthracenyl, these would bethe 1- and 8-positions.

The term “variable denticity” is used herein in the context of otherwisebidentate ligands to refer to the reversible formation of a thirdbinding interaction between the ligand and the Group 8-10 transitionmetal center to which it is complexed.

The abbreviation “acac” refers to acetylacetonate. In general,substituted acetylacetonates, wherein one or more hydrogens in theparent structure have been replaced by a hydrocarbyl, substitutedhydrocarbyl, or fluoroalkyl, may be used in place of the “acac”.Hydrocarbyl substituted acetylacetonates may be preferred in some caseswhen it is important, for example, to improve the solubility of a(ligand)Ni(acac)BF₄ salt in mineral spirits.

The phrase “an amount of hydrogen effective to achieve chain transfer”refers to the ability of hydrogen to react with an olefin polymerizationcatalyst to cleave off a growing polymer chain and initiate a new chain.In most cases, this is believed to involve hydrogenolysis of themetal-carbon bond of the growing polymer chain, to form a metal hydridecatalytic intermediate, which can then react with the olefin monomer toinitiate a new chain. In the context of the current invention, aneffective amount is considered to be that amount of hydrogen whichreduces both the number average molecular weight and the weight averagemolecular weight of the polymer by at least 10%, relative to anotherwise similar reaction conducted in the absence of hydrogen. In thiscontext, “otherwise similar” denotes that the catalyst, catalystloading, solvent, solvent volume, agitation, ethylene pressure,co-monomer concentration, reaction time, and other process relevantparameters are sufficiently similar that a valid comparison can be made.

In general, previously reported catalysts lacking the novel ortho-arylsubstitution pattern of the current invention are far less productive inthe presence of an amount of hydrogen effective to achieve chaintransfer than they are under otherwise similar conditions withouthydrogen. In order to quantify this effect, the following terms aredefined.

The productivity P is defined as the grams of polymer produced per moleof catalyst, over a given period of time. The productivity P_(hydrogen)is defined as the grams of polymer produced per mole of catalyst in thepresence of an amount of hydrogen effective to achieve chain transfer,in an otherwise similar reaction conducted for the same period of time.Catalysts lacking the novel ortho-aryl substitution pattern of thecatalyst compositions of the current invention typically exhibit ratiosP_(hydrogen)/P less than or equal to 0.05 under substantially non-masstransport limited conditions.

The phrase “improved stability in the presence of an amount of hydrogeneffective to achieve chain transfer” means that the ratio P_(hydrogen)/Pis at least 0.1 under substantially non-mass transport limitedconditions. Preferred catalysts of the present invention exhibit a ratioP_(hydrogen)/P greater than or equal to 0.2 under substantially non-masstransport limited conditions. Especially preferred catalysts of thepresent invention exhibit a ratio P_(hydrogen)/P greater than or equalto 0.5 under substantially non-mass transport limited conditions.

The phrase “one or more olefins” refers to the use of one or morechemically different olefin monomer feedstocks, for example, ethyleneand propylene.

The phrase “capable of inserting an olefin” refers to a group Z bondedto the transition metal M, which can insert an olefin monomer of thetype R^(1a)CH═CHR^(1b) to form a moiety of the typeM—CHR^(1a)—CHR^(1b)—Z, which can subsequently undergo further olefininsertion to form a polymer chain; wherein R^(1a) and R^(1b) mayindependently be H, hydrocarbyl, substituted hydrocarbyl, fluoroalkyl,silyl, O(hydrocarbyl), or O(substituted hydrocarbyl), and wherein R^(1a)and R^(1b) may be connected to form a cyclic olefin, provided that inall cases, the substituents R^(1a) and R^(1b) are compatible with thedesired catalysis; wherein additional groups will be bound to thetransition metal M to comprise the actual catalyst, as discussed in moredetail below.

The degree of steric hindrance at the active catalyst site required togive slow chain transfer, and thus form polymer, depends on a number offactors and is often best determined by experimentation. These factorsinclude: the exact structure of the catalyst, the monomer or monomersbeing polymerized, whether the catalyst is in solution or attached to asolid support, and the temperature and pressure. The term “polymer” isdefined herein as corresponding to a degree of polymerization, DP, ofabout 10 or more; oligomer is defined as corresponding to a DP of 2 toabout 10.

The term “total productivity” is defined in the context of ethylenepolymerization as the number of kilograms of polyethylene per mole ofcatalyst and is the maximum weight of polyethylene that can be producedusing a given catalyst.

By “suitable counterions”, we mean weakly coordinating ions withsufficient charge to give the overall catalyst complex no net charge.

In the context of structures kk1 and kk2, “ancillary ligands” are atomsor groups which serve to satisfy the valency of M¹ without interferingwith the desired catalysis.

The compounds of Sets 18-21 and formula ii1 may be prepared as describedin the examples contained herein, or by methods described in thereferences cited by Ittel et al. (Chem. Rev. 2000, 100, 1169); or inU.S. patent application Ser. No. 09/507,492, filed on Feb. 18, 2000,Ser. No. 09/563,812, filed on May 3, 2000, and Ser. No. 09/231,920,filed on Sep. 11, 2000; or in U.S. Provisional Application Nos.60/246,254, 60/246,255, and 60/246,178, all filed on Nov. 6, 2000.

A variety of protocols may be used to generate active polymerizationcatalysts comprising transition metal complexes of various nitrogen,phosphorous, oxygen and sulfur donor ligands. Examples include: (i) thereaction of a Ni(II), Pd(II), Co(II) or Fe(II) dihalide complex of abidentate N,N-donor ligand with an alkylaluminum reagent, for example,the reaction of (bidentate N,N-donor ligand)Ni(acac)X salts with analkylaluminum reagent, where X is a weakly coordinating anion, such asB(C₆F₅)₄ ⁻, BF₄ ⁻, PF₆ ⁻, SbF₆ ⁻ and OS(O)₂CF₃ ⁻, (ii) the reaction of abidentate N,N-donor ligand with bis(1,5-cyclooctadiene)nickel(0) and[H(OEt₂)₂]⁺[B(3,5-(CF₃)₂C₆H₃)₄]⁻, and (iii) the reaction of a bidentateN,N-donor ligand with bis(1,5-cyclooctadiene)nickel(0) and B(C₆F₅)₃.Cationic [(ligand)M(π-allyl)]⁺ complexes with weakly coordinatingcounteranions, where M is a Group 10 transition metal, are often alsosuitable catalyst precursors, requiring only exposure to olefin monomerand in some cases elevated temperatures (40-100° C.) or added Lewisacid, or both, to form an active polymerization catalyst.

More generally, a variety of (ligand)_(n)M(Z^(1a))(Z^(1b)) complexes,where “ligand” refers to a compound of the present invention and is abidentate or variable denticity ligand comprising one or two nitrogendonor atom or atoms independently substituted by an aromatic orheteroaromatic ring(s), wherein the ortho positions of the ring(s) aresubstituted by aryl or heteroaryl groups, n is 1 or 2, M is a Group 8-10transition metal, and Z^(1a) and Z^(1b) are univalent groups, or may betaken together to form a divalent group, may be reacted with one or morecompounds, collectively referred to as compound Y¹, which function asco-catalysts or activators, to generate an active catalyst of the form[(ligand)_(n)M(T^(1a))(L)]⁺X⁻, where n is 1 or 2, T^(1a) is a hydrogenatom or hydrocarbyl, L is an olefin or neutral donor group capable ofbeing displaced by an olefin, M is a Group 8-10 transition metal, and X⁻is a weakly coordinating anion. When Z^(1a) and Z^(1b) are both halide,examples of compound Y¹ include: methylaluminoxane (herein MAO) andother aluminum sesquioxides, R₃Al, R₂AlCl, and RAlCl₂ (wherein R isalkyl, and plural groups R may be the same or different). When Z^(1a)and Z^(1b) are both alkyl, examples of a compound Y¹ include: MAO andother aluminum sesquioxides, R₃Al, R₂AlCl, RAlCl₂ (wherein R is alkyl,and plural groups R may be the same or different), B(C₆F₅)₃, R⁰ ₃Sn[BF₄](wherein R⁰ is hydrocarbyl or substituted hydrocarbyl and plural groupsR⁰ may be the same or different), H⁺X⁻, wherein X is a weaklycoordinating anion, for example, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and Lewis acidic or Bronsted acidicmetal oxides, for example, montmorillonite clay. In some cases, forexample, when Z^(1a) and Z^(1b) are both halide or carboxylate,sequential treatment with a metal hydrocarbyl, followed by reaction witha Lewis acid, may be required to generate an active catalyst. Examplesof metal hydrocarbyls include: MAO, other aluminum sesquioxides, R₃Al,R₂AlCl, RAlCl₂ (wherein R is alkyl, and plural groups R may be the sameor different), Grignard reagents, organolithium reagents, anddiorganozinc reagents. Examples of Lewis acids include: MAO, otheraluminum sesquioxides, R₃Al, R₂AlCl, RAlCl₂ (wherein R is alkyl, andplural groups R may be the same or different), B(C₆F₅)₃, R⁰ ₃Sn[BF₄](wherein R⁰ is hydrocarbyl or substituted hydrocarbyl and plural groupsR⁰ may be the same or different), and Lewis acidic metal oxides.

The foregoing discussion is intended to illustrate that there arefrequently many ways to generate an active catalyst. There are a varietyof methods wherein the ligands of the present invention can be reactedwith a suitable metal precursor, and optionally a co-catalyst, togenerate an active olefin polymerization catalyst. Without wishing to bebound by theory, we believe that the active catalyst typically comprisesthe catalytically active metal, one or more ligands of the presentinvention, the growing polymer chain (or a hydride capable of initiatinga new chain), and a site on the metal adjacent to the metal-alkyl bondof said chain where ethylene can coordinate, or at least closelyapproach, prior to insertion. Where specific structures for activecatalysts have been implied herein, it should be understood that activecatalysts comprising the ligands of the present invention are formed asthe reaction products of the catalyst activation reactions disclosedherein, regardless of the detailed structures of those active species.

In some cases, it is advantageous to attach the catalyst to a solidsupport. Examples of useful solid supports include: inorganic oxides,such as talcs, silicas, titania, silica/chromia, silica/chromia/titania,silica/alumina, zirconia, aluminum phosphate gels, silanized silica,silica hydrogels, silica xerogels, silica aerogels, montmorillonite clayand silica co-gels, as well as organic support materials such aspolystyrene and functionalized polystyrene. (See, for example, S. B.Roscoe et al., “Polyolefin Spheres from Metallocenes Supported onNon-Interacting Polystyrene,” 1998, Science, 280, 270-273 (1998)).

Thus, in a preferred embodiment, the catalysts of the present inventionare attached to a solid support (by “attached to a solid support” ismeant ion paired with a component on the surface, adsorbed to thesurface or covalently attached to the surface) that has been pre-treatedwith a compound Y¹. More generally, the compound Y¹ and the solidsupport can be combined in any order and any number of compound(s) Y¹can be utilized. In addition, the supported catalyst thus formed may betreated with additional quantities of compound Y¹. In another preferredembodiment, the compounds of the present invention are attached tosilica that has been pre-treated with an alkylaluminum compound Y¹, forexample, MAO, Et₃Al, ^(i)Bu₃Al, Et₂AlCl, or Me₃Al.

Such supported catalysts are prepared by contacting the transition metalcompound, in a substantially inert solvent (by which is meant a solventwhich is either unreactive under the conditions of catalyst preparation,or if reactive, acts to usefully modify the catalyst activity orselectivity) with MAO-treated silica for a sufficient period of time togenerate the supported catalyst. Examples of substantially inertsolvents include toluene, o-difluorobenzene, mineral spirits, hexane,CH₂Cl₂, and CHCl₃.

In another preferred embodiment, the catalysts of the present inventionare activated in solution under an inert atmosphere, and then adsorbedonto a silica support which has been pre-treated with a silylating agentto replace surface silanols by trialkylsilyl groups. Methods topre-treat silicas in this way are known to those skilled in the art andmay be achieved, for example, by heating the silica withhexamethyldisilazane and then removing the volatiles under vacuum. Avariety of precurors and procedures may be used to generate theactivated catalyst prior to said adsorption, including, for example,reaction of a (ligand)Ni(acac)B(C₆F₅)₄ complex with Et₂AlCl in atoluene/hexane mixture under nitrogen; where “ligand” refers to acompound of the present invention.

The polymerizations may be conducted in batch or continuous processes,as solution polymerizations, as non-solvent slurry type polymerizations,as slurry polymerizations using one or more of the olefins or othersolvent as the polymerization medium, or in the gas phase. One ofordinary skill in the art, with the present disclosure, would understandthat the catalyst could be supported using a suitable catalyst supportand methods known in the art. Substantially inert solvents, such astoluene, hydrocarbons, methylene chloride and the like, may be used.Propylene and 1-butene are excellent monomers for use in slurry-typecopolymerizations and unused monomer can be flashed off and reused.

Temperature and olefin pressure have significant effects on polymerstructure, composition, and molecular weight. Suitable polymerizationtemperatures are preferably from about 20° C. to about 160° C., morepreferably 60° C. to about 100° C. Suitable polymerization pressuresrange from about 1 bar to 200 bar, preferably 5 bar to 50 bar, and morepreferably from 10 bar to 50 bar.

The catalyst concentration in solution, or loading on a support, isadjusted to give a level of activity suitable for the process anddesired polymer. In the case of solution phase or a slurry phase processusing a soluble catalyst precursor, suitable catalyst concentrations aretypically in the range of 0.01 to 100 micromoles/L, preferably 0.1 to 10micromoles/L, even more preferably 0.2 to 2 micromoles/L. Higherloadings tend to reduce the solution phase concentration of ethylene ata given temperature, pressure and agitation rate, and can thereforeresult in relatively more chain running and branching in some cases.

In some cases, it is possible that the catalysts of the presentinvention may acquire new hydrocarbyl substituents, attached to theligand or counteranion, or both, under the conditions of the olefinpolymerization reaction. For example, if a bidentate N,N-donor ligand ofthe current invention underwent cyclometallation to form a tridentateligand with a nickel-carbon bond, insertion of one or more ethylenesinto this bond, followed by hydrogenolysis or by β-H elimnation, couldresult in a new hydrocarbyl side chain attached to said ligand.Alternatively, the ligand could comprise an olefinic side chainsubstituent prior to polymerization, and this side chain could undergocopolymerization in the presence of ethylene to attach an oligomeric orpolymeric group to the ligand. It is also possible that the reactionproduct of (i) bis(1,5-cyclooctadiene)nickel(0), (ii) a ligand of thepresent invention and (iii) B(C₆F₅)₃ may comprise acycloctadiene-derived hydrocarbyl bridge between cationic nickel andanionic boron, and subsequent ethylene insertion may result in theattachment of a polyethylene chain to the borate counteranion.Therefore, although hydrocarbyl groups attached to the ligand orcounteranion of the current invention will generally be relatively lowmolecular weight groups (less than about MW=500), it is possible thatthey will be modified as described above under some olefinpolymerization reaction conditions, and any such modified catalysts arealso considered within the scope of this invention.

The catalysts of the present invention may be used alone, or incombination with one or more other Group 3-10 olefin polymerization oroligomerization catalysts, in solution, slurry, or gas phase processes.Such mixed catalysts systems are sometimes useful for the production ofbimodal or multimodal molecular weight or compositional distributions,which may facilitate polymer processing or final product properties.

After the reaction has proceeded for a time sufficient to produce thedesired polymers, the polymer can be recovered from the reaction mixtureby routine methods of isolation and/or purification.

In general, the polymers of the present invention are useful ascomponents of thermoset materials, as elastomers, as packagingmaterials, films, compatibilizing agents for polyesters and polyolefins,as a component of tackifying compositions, and as a component ofadhesive materials.

High molecular weight resins are readily processed using conventionalextrusion, injection molding, compression molding, and vacuum formingtechniques well known in the art. Useful articles made from them includefilms, fibers, bottles and other containers, sheeting, molded objectsand the like.

Low molecular weight resins are useful, for example, as synthetic waxesand they may be used in various wax coatings or in emulsion form. Theyare also particularly useful in blends with ethylene/vinyl acetate orethylene/methyl acrylate-type copolymers in paper coating or in adhesiveapplications.

Although not required, typical additives used in olefin or vinylpolymers may be used in the new homopolymers and copolymers of thisinvention. Typical additives include pigments, colorants, titaniumdioxide, carbon black, antioxidants, stabilizers, slip agents, flameretarding agents, and the like. These additives and their use in polymersystems are known per se in the art.

Other features of the invention will become apparent in the followingdescription of working examples, which have been provided forillustration of the invention and are not intended to be limitingthereof.

The molecular weight data presented in the following examples isdetermined at 135° C. in 1,2,4-trichlorobenzene using refractive indexdetection, calibrated using narrow molecular weight distributionpoly(styrene) standards.

EXAMPLES Example 1 Synthesis of aaa1

To a 500 mL round bottomed flask equipped with a magnetic stir bar wasadded 25 g (141.8 mmol) of 4′-tert-butylacetophenone and 7.52 g (70.9mmol) of benzaldehyde. The solution was stirred and 20.9 mL (170.2 mmol)of boron trifluoride diethyl etherate was added dropwise. The solutionwas stirred for 1 h at room temperature then the reaction vessel waslowered into a preheated oil bath at 90° C. and stirred for 2 h. Thereaction vessel was allowed to cool to room temperature then poured into500 mL of diethyl ether. The product precipitated from solution and wasisolated by suction filtration. The filter cake was washed with 100 mLof diethyl ether then dried under vacuum to give 11.30 g (31%) of aaa1as a yellow solid. ¹H NMR (DMSO-d₆, 300 MHz) δ1.40 (s, 18H), 7.81 (d,J=8.8 Hz, 4H), 7.82 (m, 3H), 8.50 (d, J=8.3 Hz, 4 H), 8.57 (d, J=7.7 Hz,2 H), 9.08 (s, 2H).

Example 2 Synthesis of aaa2

To a 500 mL round bottomed flask equipped with a magnetic stir bar and areflux condenser was added 11.0 g (21.7 mmol) of aaa1, 100 mL ofanhydrous ethanol, and 1.7 mL (32.5 mmol) of nitromethane. The mixturewas stirred and 9.1 mL (65.1 mmol) of triethylamine was added over 3minutes. The reaction vessel was lowered into a preheated oil bath at110° C. and allowed to reflux under nitrogen. After 1 h the reactionvessel was allowed to cool to room temperature and 100 mL of methanolwas added to precipitate the product. The product was collected bysuction filtration, washed with 100 mL of methanol and dried undervacuum to give 6.42 g (64%) of aaa2 as a white solid. ¹H NMR (CDCl₃, 300MHz) δ1.36 (s, 18 H), 7.43 (m, 11 H), 7.62 (s, 2H), 7.62 (m, 1H), 7.64(m, 1H).

Example 3 Synthesis of aaa3

To a 300 mL Parr shaker vessel was added 6.4 g (13.8 mmol) of aaa2 and aslurry of 1.28 g of 5% Pd/C in 50 mL of DMF followed by 30 mL ofmethanol. The reaction vessel was purged with nitrogen three times,heated to 50° C. and shaken under 55 psi of hydrogen for 12 h. Thereaction vessel was purged with nitrogen then allowed to cool to roomtemperature. The mixture was filtered through Celite and the Celite padwas washed with 100 ml of methylene chloride. The solution wasconcentrated to remove the methylene chloride then 400 mL of methanolwas added to precipitate the product. The product was collected bysuction filtration and washed with 100 mL of methanol to give 5.46 g(91%) of aaa3 as a white crystalline solid. ¹H NMR (CDCl₃, 300 MHz)δ1.39 (s, 18H), 3.98 (s, 2H), 7.26 (m, 2H), 7.40 (m, 4H), 7.51 (m, 7H),7.60 (m, 2H).

Example 4 Synthesis of aaa4

To a 500 mL round bottomed flask equipped with a magnetic stir bar wasadded 50 g (373 mmol) of 4′-methylacetophenone and 19.77 g (186.3 mmol)of benzaldehyde. The solution was stirred and 56.7 mL (447.12 mmol) ofboron trifluoride diethyl etherate was added dropwise. The solution wasstirred for 30 min at room temperature then the reaction vessel waslowered into a preheated oil bath at 90° C. and stirred for 2 h. Thereaction vessel was allowed to cool to room temperature then poured into1 L of diethyl ether. The product precipitated from solution and wasisolated by suction filtration. The filter cake was washed with 500 mLof diethyl ether then dried under vacuum to give 27.85 g (35%) of aaa4as a yellow solid. ¹H NMR (CDCl₃, 300 MHz) δ2.5 (s, 6H), 7.59 (d, J=7.9Hz, 4H), 7.72 (m, 2H), 7.86 (m, 1H), 8.47 (d, J=8.4 Hz, 4H), 8.56 (d,J=7.3 Hz, 2H), 9.04 (s, 2H).

Example 5 Synthesis of aaa5

To a 300 mL round bottomed flask equipped with a magnetic stir bar and areflux condenser was added 27.0 g (63.7 mmol) of aaa4, 100 mL ofanhydrous ethanol, and 4.92 mL (95.5 mmol) of nitromethane. The mixturewas stirred and 26.6 mL (191.1 mmol) of triethylamine was added. Thereaction vessel was lowered into a preheated oil bath at 110° C. andallowed to reflux under nitrogen. After 2.5 h the reaction vessel wasallowed to cool to room temperature and concentrated to an oil. The oilwas purified by silica gel chromatography (20% methylene chloride inhexane) to give 14.93 g (62%) of aaa5 as a colorless oil thatcrystallized upon standing. ¹H NMR (CDCl₃, 300 MHz) δ2.41 (s, 6H), 7.26(d, J=7.8 Hz, 4H), 7.36 (d, J=7.9 Hz, 4H), 7.46 (m, 3H), 7.61 (s, 2H),7.64 (m, 2H).

Example 6 Synthesis of aaa6

To a 300 mL Parr shaker vessel was added 17.6 g (46.4 mmol) of aaa5 anda slurry of 1.76 g of 5% Pd/C in 60 mL of DMF followed by 30 mL ofmethanol. The reaction vessel was purged with nitrogen three times,heated to 50° C. and shaken under 55 psi of hydrogen for 6 h. Thereaction vessel was purged with nitrogen then allowed to cool to roomtemperature. The mixture was filtered through Celite and the Celite padwas washed with 100 ml of methylene chloride. The solution wasconcentrated to remove the methylene chloride then 500 mL of methanolwas added to precipitate the product. The product was collected bysuction filtration and washed with 100 mL of methanol to give 16.18 g(100%) of aaa6 as a white crystalline solid. ¹H NMR (CDCl₃, 300 MHz)δ2.49 (s, 6H), 3.99 (s, 2H), 7.34 (m, 1H), 7.36 (d, J=7.5 Hz, 4H), 7.44(d, J=8.0 Hz), 7.48 (s, 2H), 7.54 (d, J=7.8 Hz, 4H), 7.67 (d, J=8.1 Hz,2H).

Example 7 Synthesis of aaa7

Pyridine (25 mL) was added to a 100 mL round bottomed flask equippedwith a magnetic stir bar followed by 8.20 g (23.5 mmol) of aaa6. Themixture was stirred and 1.03 mL (11.75 mmol) of oxalyl chloride wasadded dropwise. The mixture was stirred for 2 h at room temperature thenpoured into 400 mL of methanol to precipitate the product. The productwas isolated by suction filtration, washed with 100 mL of methanol thendried under vacuum to give 5.28 g (60%) of aaa7 as a light blue solid.¹H NMR (CDCl₃, 300 MHz) δ2.47 (s, 12H), 7.21 (s, 16H), 7.45 (m, 6H),7.62 (s, 4H), 7.66 (d, J=7.4 Hz, 4H), 8.71 (s, 2H).

Example 8 Synthesis of aaa8

To a 250 mL round bottomed flask equipped with a magnetic stir bar wasadded 5.25 g (6.98 mmol) of aaa7, 100 mL of o-xylene, and 3.10 g ofP₄S₁₀. The reaction vessel was lowered into a preheated oil bath at 150°C. and stirred under nitrogen for 1 h. The reaction vessel was allowedto cool to room temperature then poured into 400 mL of methanol toprecipitate the product. The product was isolated by suction filtrationthen washed with 100 mL of methanol then dried under vacuum to give 5.11g (94%) of aaa8 as orange crystals. ¹H NMR (CDCl₃, 300 MHz) δ2.44 (s,12H), 7.13 (d, J=7.9 Hz, 8H), 7.21 (d, J=8.5 Hz, 8H), 7.41 (m, 6H), 7.61(s, 4H), 7.65 (m, 4H), 11.2 (s, 2H).

Example 9 Synthesis of aaa9

To a 100 mL round bottomed flask equipped with a magnetic stir bar wasadded 5.00 g (6.38 mmol) of aaa8, 10 mL of 1,2-dibromoethane, and 10 mLof 6.4 M NaOH solution followed by 409 mg (1.27 mmol) oftetrabutylammonium bromide. The mixture was stirred for 15 minutes thenpoured into 150 mL of methanol to give an oil that gradually solidified.The solid was isolated by suction filtration, crushed with a spatulathen washed with 50 mL of methanol and dried under vacuum to give 5.14 g(100%) of aaa9 as a tan solid. ¹H NMR (CDCl₃, 300 MHz) δ2.16 (s, 4H),2.70 (s, 12H), 7.10 (d, J=7.9 Hz, 8H), 7.42 (m, 14 H), 7.62 (s, 4H),7.69 (d, J=7.3 HZ, 4H).

Example 10 Synthesis of aaa10

A suspension of dibenzoyl ethane (8.8 g, 37 mmol) in toluene (15 ml) and1-methyl-2-pyrrolidinone (7.5 ml) was treated with oxalic dihydrazide (2g, 17 mmol). The flask was fitted with a Dean Stark trap, and immersedin a 170° C. oil bath. The resulting suspension was stirred under Ar,with azeotropic removal of water until all of the starting diketone wasconsumed (determined by TLC), then cooled to rt. The solvent was removedin vacuo. The dark oily residue was washed with MeOH and filtered toafford a mixture (4.21 g) of N,N′-bis(2,5-diphenyl-1-pyrrolyl) oxamidecontaminated with an unidentified impurity (on the order of 50-65% byweight), which was used without purification.

Example 11 Synthesis of aaa11

A suspension of impure aaa10 from Example 10 (523 mg) in ortho-xylene (6ml) was treated with phosphorus pentasulfide (222 mg, 0.5 mmol). Theflask was fitted with a reflux condenser, and immersed in a 180° C. oilbath. The resulting suspension was refluxed under nitrogen for ca. 2 h,then cooled to rt, then diluted with ca. 35 mL methylene chloride. Theheterogeneous mixture was poured onto a column of silica (10″×50 mm) andeluted with methylene chloride/toluene (3/2), collecting only theforerunning orange-red band. The solvent was removed in vacuo to giveaaa11 as deep violet needles (yield 121 mg).

Example 12 Synthesis of aaa12

A suspension of aaa11 (566 mg, 1.02 mmol) in 1,2-dibromoethane (7 ml)was treated with tetrabutylammonium bromide (15 mg) and 2 N aq NaOH (10mL). The biphasic mixture was stirred vigorously for 15 min. The colordischarged markedly and a pale precipitate separated almost immediatelyon stirring. The mixture was diluted with methylene chloride (200 mL)and water (200 mL). The layers were separated, and the organic layer waswashed with water (2×50 mL) and dried (MgSO₄), concentrated, andadsorbed onto silica, then chromatographed over silica eluting withmethylene chloride/hexane. The solvent was removed in vacuo to giveaaa12 as an orange-yellow powder (yield 520 mg).

Example 13 Synthesis of aaa13

aaa3 (5.1 g, 11.76 mmol) was dissolved in pyridine (5 mL) and treatedwith 4-(dimethylamino)-pyridine (30 mg). Under an atmosphere of drynitrogen gas, oxalyl chloride (515 mL, 5.88 mmol) was added dropwise.The mixture was stirred ca. 72 h at rt, then heated to 60° C. for 2 hmore. After cooling to rt, tlc analysis indicated that some of theaniline remained unreacted, but the desired product was the majorcomponent of the reaction mixture. The reaction mixture was treated withmethanol to precipitate the desired product. The white powder wascollected by vacuum filtration, and washed with methanol to afford 4.4 gaaa13.

Example 14 Synthesis of aaa14

A suspension of aaa13 (4.4 g, 4.78 mmol) in ortho-xylene (20 ml) wastreated with phosphorus pentasulfide (1.1 g, 2.39 mmol). The flask wasfitted with a reflux condenser, and immersed in a 180° C. oil bath. Theresulting suspension was refluxed under nitrogen for ca. 3 h, thencooled to rt, then diluted with ca. 35 mL methylene chloride. Theheterogeneous mixture was poured onto a column of silica (10″×50 mm) andeluted with methylene chloride/hexane, collecting only the forerunningorange band. Upon concentration, aaa14 crystallized from solution asorange needles (2 g), and was collected by filtration. The filtrate wasconcentrated to give more aaa14 as an orange crystalline powder (1.8 g).

Example 15 Synthesis of aaa15

A suspension of aaa14 (2 g, 2.1 mmol) in 1,2-dibromoethane (7 ml) wastreated with tetrabutylammonium bromide (15 mg) and 2 N aq NaOH (10 mL).The biphasic mixture was stirred vigorously for 1.5 h. The colordischarged markedly and a pale precipitate separated. The mixture wasdiluted with methylene chloride (200 mL) and water (200 mL). The layerswere separated, and the organic layer was washed with water (2×50 mL).The organic layer was concentrated to 50 mL, the treated with methanol.aaa15 crystallized as short pale yellow needles (1.19 g, 1^(st) crop). Asecond crop eventually crystallized from the filtrate (0.66 g). A thirdcrop was obtained by treating the filtrate of the second with a few mLsof water (110 mg).

Example 16 Synthesis of bbb1

In an argon filled glove box, aaa15, (98.0 mg, 0.100 mmol),nickel(II)acetonylacetonate (25.7 mg, 0.100 mmol), andtriphenylcarbenium tetrakis(pentafluorophenyl)borate (92.3 mg, 0.100mmol) were weighed to a Schlenk flask. On the Schlenk line, 10 mL drydiethyl ether was added to give a dark red solution. Dry hexane (4 mL)was added and dark crystals separated. The supernatant was removed viafiler paper-tipped cannula. The dark bronze crystals were washed (2×10mL) with a hexane/ether (1/1) mixture, then dried several hours in vacuoto afford 163.3 mg (89%) bbb1.

Example 17 Synthesis of bbb2

Ligand aaa9 (1.00 g) was treated with nickel(II)acetonylacetonate andtriphenylcarbenium tetrakis(pentafluorophenyl)borate according to theprocedure given in Example 16 to afford 1.71 g (84%) bbb2.

Example 18 Preparation of a Heterogeneous Catalyst Comprising Ligand a54

To a vial charged with a54 (23 mg; 44 μmol), Ni(acac)₂ (12.8 mg; 49.8μmol) and Ph₃CB(C₆F₅)₄ (46.2 mg; 50 μmol) was added 0.8 mLdichloromethane. The resulting solution was stirred for a few hours andsubsequently added dropwise to silica (0.5 g; Grace Davison Sylopol2100). Volatiles were then removed under vacuum to give the desiredproduct.

Example 19 Polymerization of Ethylene Using the Catalyst Prepared inExample 18

A catalyst delivery device was charged with the catalyst prepared inExample 18 (2.5 mg; 0.19 μmol Ni, dispersed in 130 mg Grace DavisonXPO-2402 silica) and fixed to the head of a 1000-mL Parr® reactor. Thedevice was placed under vacuum. The reactor was then charged with NaCl(298 g) that had been dried in vacuum at 130° C. for several hours,closed, evacuated and backfilled with nitrogen five times. The leak rateof the reactor was tested by pressurizing to ca. 200 psi C₂H₄ for 5 min.The reactor was then depressurized, and the salt treated withtrimethylaluminum (10 mL; 2.0 M in hexane) and agitated at 75° C. for 30min. The reactor was subsequently pressurized with ethylene (200 psi)and depressurized to atmospheric pressure three times. The catalyst wasthen introduced in the reactor with appropriate agitation. The reactionwas allowed to proceed for 60 min at 75° C. The reactor was thendepressurized. The polymer was isolated by washing the content of thereactor with hot water. The isolated polymer was further treated with 6M HCl in methanol, rinsed with methanol and dried under vacuum to give5.72 g (1,000,000 TO; 2240 g polymer/g catalyst; GPC: M_(n)=65,400,M_(w)/M_(n)=3.4; ¹H NMR: 10 BP/1000C; T_(m)=122° C.).

Example 20 Preparation of a Heterogeneous Catalyst Comprising Ligand aa1

A solution of aa1 (73.6 mg) was dissolved in 0.75 mL dichloromethane andadded dropwise to 0.50 g silica (Grace Davison XPO-2402). The volatileswere removed in vacuo (1.5 h) at room temperature. The resulting solidwas used as such in subsequent polymerizations.

Example 21 Polymerization of Ethylene Using the Catalyst Prepared inExample 20

A catalyst delivery device was charged with the catalyst prepared inExample 20 (3.8 mg; 0.33 μmol Ni) dispersed in 122 mg silica (GraceDavison XPO-2402) and fixed to the head of a 1000-mL Parr® reactor. Thedevice was placed under vacuum. The reactor was then charged with NaCl(315 g) that had been dried in vacuum at 130° C. for several hours,closed, evacuated and backfilled with nitrogen five times. The leak rateof the reactor was tested by pressurizing to ca. 200 psi C₂H₄ for ca. 5min. The reactor was then depressurized, and the salt treated withtrimethylaluminum (10 mL; 2.0 M in hexane) and agitated at 86° C. for 30min. The reactor was subsequently pressurized with ethylene (200 psi)and depressurized to atmospheric pressure three times. The catalyst wasthen introduced in the reactor with appropriate agitation. The reactionwas allowed to proceed for 240 min at 90 C. The reactor was thendepressurized. The polymer was isolated by washing the content of thereactor with hot water. The isolated polymer was further treated with 6M HCl in methanol, rinsed with methanol and dried under vacuum to give8.1 g (850,000 TO; 2100 g polymer/g catalyst; GPC: partially insoluble;¹H NMR: 11.7 BP/1000C; T_(m)=111.2 C.).

Example 22

Polymerization of Ethylene Using the Catalyst Prepared in Example 20,with Hydrogen as a Chain-transfer Agent

A catalyst delivery device was charged with the catalyst prepared inExample 20 (3.8 mg; 0.33 μmol Ni) dispersed in 122 mg silica (GraceDavison XPO-2402) and fixed to the head of a 1000-mL Parr® reactor. Thedevice was placed under vacuum. The reactor was then charged with NaCl(372 g) that had been dried in vacuum at 130° C. for several hours,closed, evacuated and backfilled with nitrogen five times. The salt wasthen treated with trimethylaluminum (10 mL; 2.0 M in hexane) andagitated at 85° C. for 30 min. The reactor was subsequently pressurizedwith ethylene (200 psi) and depressurized to atmospheric pressure threetimes. The catalyst was then introduced in the reactor with appropriateagitation. The reaction was allowed to proceed for 30 min at 85 C. Thereactor was then depressurized and hydrogen (100 mL) was added viasyringe. The reactor was then repressurized with ethylene (200 psi) andthe reaction allowed to proceed for an additional 210 min. The reactorwas depressurized to atmospheric pressure. The polymer was isolated bywashing the content of the reactor with hot water. The resulting polymerwas further treated with 6 M HCl in methanol, rinsed with methanol anddried under vacuum to give 4.41 g (278,000 TO; 686 g polymer/g catalyst;GPC: M_(n)=70,100, M_(w)=589,000. (The chromatogram was bimodal withM_(p)=2,700,000 and 200,000.)

Example 23 Polymerization of Ethylene Using the Catalyst Prepared inExample 20, with Hydrogen as a Chain-transfer Agent

A catalyst delivery device was charged with the catalyst prepared inExample 20 (14.9 mg; 1.3 μmol Ni) dispersed in 152 mg silica (GraceDavison XPO-2402) and fixed to the head of a 1000-mL Parr® reactor. Thedevice was placed under vacuum. The reactor was then charged with NaCl(363 g) that had been dried in vacuum at 130° C. for several hours,closed, evacuated and backfilled with nitrogen five times. The salt wasthen treated with trimethylaluminum (10 mL; 2.0 M in hexane) andagitated at 85° C. for 30 min. The reactor was subsequently pressurizedwith ethylene (200 psi) and depressurized to atmospheric pressure threetimes. Hydrogen (100 mL) was then syringed in the reactor and thereactor subsequently repressurized to 600 psi ethylene as the catalystwas introduced in the reactor with appropriate agitation. The reactionwas allowed to proceed for 30 min at 89° C. The reactor was thendepressurized to atmospheric pressure. The polymer was isolated bywashing the content of the reactor with hot water. The resulting polymerwas further treated with 6 M HCl in methanol, rinsed with methanol anddried under vacuum to give 26.2 g (1,300,000 TO; 1750 g polymer/gcatalyst; GPC: M_(n)=179,000, M_(w)=717,000).

Example 24 Preparation of a Heterogeneous Catalyst Comprising Ligandaaa16

Ph₃CB(C₆F₅)₄ (14.5 mg; 15.7 μmol) was added to a solution of aaa16 (12.6mg; 16.0 μmol, prepared by methods similar to those described above,from the 2,6-diphenyl-4-(4-methoxyphenyl)-aniline, with the methoxygroup being de-O-methylated as the last step) and Ni(acac)₂ (4.1 mg; 16μmol) in acetone to result in a Ni concentration of 9.4 μmol/mL. Analiquot (0.75 mL) of the resulting solution was collected and thevolatiles removed in vacuo. The residue was taken up in 1.0 mLdichloromethane, resulting in a Ni concentration of 7.1 μmol/mL. To analiquot of this solution (0.70 mL; 5.0 μmol) was addedtetramethyldisilazane (5.3 μmol) and further diluted withdichloromethane to afford 6.4 μmol/mL. A volume of this solution,equivalent to 1.9 μmol Ni, was diluted with dichloromethane to reach aconcentration of 3.33 μmol/mL. The resulting solution was then addeddropwise to silica (381 mg; Grace Davison XPO-2402). The resulting solidwas stored at room temperature for several hours (ca. 18 h) prior toadding toluene (50 mL). The mixture was stirred for 60 min and thesupernatant removed with a cannula equipped with a filter. The residualsolid was further washed with toluene (2×25 mL) and then dried in vacuoto give an orange solid, used as such in subsequent polymerizationexperiments.

Example 25 Polymerization of Ethylene Using the Catalyst Prepared inExample 24

A 600-mL Parr® reactor was charged with the catalyst prepared in Example24. Toluene (150 mL) was added to the reactor before pressurizing to 200psi ethylene to saturate the mixture. The reactor was then depressurizedand MMAO type 4 (1.5 mL; 7.14 wt % Al; Akzo Nobel) was added. Thereactor was repressurized with ethylene (200 psi) and the temperaturequickly ramped up to 85° C. The reaction was allowed to proceed underthose conditions for 120 min before being quenched by addition ofmethanol. The mixture was treated with 6M HCl. The polymer was collectedby filtration and dried in a vacuum oven to give 1.43 g (38 gpolyethylene/g catalyst; GPC: M_(n)=1,033,000, M_(w)=2,354,000; ¹H NMR:12.7 BP/1000 C; T_(m)=114.7° C.).

Example 26 Ethylene polymerization with Nickel Catalyst Derived fromNi(acac)₂, B(C₆F₅)₃, Ph₃C(C₆F₅)₄ and Ligand a52

A 1 L Parr® autoclave, Model 4520, was dried by heating under vacuum to180 C. at 0.6 torr for 1 h, then cooled and refilled with dry nitrogen.The autoclave was charged with dry, deoxygenated hexane (450 mL) and 4.0mL of a 10 wt % solution of MMAO (modified methylalumoxane; 23%iso-butylaluminoxane in heptane; 6.42% Al). The reactor was sealed andheated to 80° C. under nitrogen, then sufficient hydrogen was added toraise the pressure by 15.5 psi, after which sufficient ethylene wasintroduced to raise the total pressure to 300 psig. A sample loopinjector was first purged with 2.0 mL dry, deoxygenated dichloromethane(injected into the reactor), and then used to inject 2.0 mL of a stocksolution (corresponding to 0.60 μmol of pro-catalyst) prepared from17.09 mL of CH₂Cl₂ and 2.91 mL of a stock solution prepared from 42 mgligand a52, 10.1 mg Ni(acac)₂, 20.0 mg B(C₆F₅)₃, 36 mg Ph₃C(C₆F₅)₄ and atotal of 23.964 g CH₂Cl₂ (with the 1^(st) three reagents being combinedin CH₂Cl₂ and then added to a solution of the trityl salt in CH₂Cl₂),followed by 2.0 mL of CH2C12, using ethylene gas to force the liquidsinto the autoclave and raise the pressure to ca. 440 psig, after whichtime the reactor was isolated and the pressure was allowed to fall toabout 370 psig. More ethylene was then reintroduced to raise thepressure back to ca. 440 psig, and the cycle was repeated. A secondinjection of 2.0 mL of the same stock solution of pro-catalyst(corresponding to another 0.60 μmol) was made at 17.5 min. The averagepressure was 402 psig, and the average temperature was 80.4° C. After100 min, the reaction was quenched by injection of MeOH, then thereactor was cooled, depressurized and opened. The polyethyleneprecipitate was recovered by filtration and dried in vacuo to obtain50.6 g white polyethylene. A similar experiment without hydrogen,conducted for 80 min, gave 32.92 g polyethylene.

Example 27 Ethylene Polymerization with bbb1

A procedure similar to that described in Example 26 was followed, using450 mL hexane, 4.0 mL MMAO, 14.0 psig hydrogen, sufficient ethylenepressure to give 660 psig total pressure, a reaction temperature of 100°C., a single injection of 0.6 μmol of bbb1 in CH₂Cl₂ solution, and areaction time of 58 min to obtain 27.0 g polyethylene, corresponding to1.61 (10)⁶ mol C2H4/mol Ni.

Example 28 Polymerization of Ethylene Using the Catalyst Prepared inExample 20 with Hydrogen as a Chain-transfer Agent

A catalyst delivery device was charged with the catalyst prepared inExample 20 (7.0 mg; 0.61 μmol Ni) dispersed in 160 mg silica (GraceDavison XPO-2402) and fixed to the head of a 1000-mL Parr® reactor. Thedevice was placed under vacuum. The reactor was then charged with NaCl(324 g) that had been dried in vacuum at 130° C. for several hours,closed, evacuated and backfilled with nitrogen five times. The salt wasthen treated with trimethylaluminum (10 mL; 2.0 M in hexane) andagitated at 85° C. for 30 min. The reactor was subsequently pressurizedwith ethylene (200 psi) and depressurized to atmospheric pressure threetimes. Hydrogen (100 mL) was added to the reactor via a syringe. Thecatalyst was then introduced in the reactor with appropriate agitation.The reaction was allowed to proceed for 30 min at 85° C. The reactor wasdepressurized to atmospheric pressure. The polymer was isolated bywashing the content of the reactor with hot water. The resulting polymerwas further treated with 6 M HCl in methanol, rinsed with methanol anddried under vacuum to give 0.67 g (30,000 TO; 73 g polymer/g catalyst;GPC: M_(n)=127,400, M_(w)=463,000; 13.9 BP/1000 C by ¹H NMR).

Example 29 Polymerization of Ethylene Using the Catalyst Prepared inExample 20, with Hydrogen as a Chain-transfer Agent

A catalyst delivery device was charged with the catalyst prepared inExample 20 (5.5 mg; 0.48 μmol Ni) dispersed in 148 mg silica (GraceDavison XPO-2402) and fixed to the head of a 1000-mL Parr® reactor. Thedevice was placed under vacuum. The reactor was then charged with NaCl(350 g) that had been dried in vacuum at 130° C. for several hours,closed, evacuated and backfilled with nitrogen five times. The salt wasthen treated with trimethylaluminum (10 mL; 2.0 M in hexane) andagitated at 85° C. for 30 min. The reactor was subsequently pressurizedwith ethylene (200 psi) and depressurized to atmospheric pressure threetimes. The catalyst was then introduced in the reactor with appropriateagitation. The reaction was allowed to proceed for 3 min at 85° C. under200 psi ethylene. The reactor was then depressurized and hydrogen (100mL) was syringed in. The reactor was then repressurized with ethylene(200 psi) and the reaction allowed to proceed for a total reaction timeof 120 min. The reactor was depressurized to atmospheric pressure. Thepolymer was isolated by washing the content of the reactor with hotwater. The resulting polymer was further treated with 6 M HCl inmethanol, rinsed with methanol and dried under vacuum to give 2.0 g(140,000 TO; 340 g polymer/g catalyst; GPC: M_(n)=81,600 M_(w)=301,800;12.4 BP/1000 C by ¹H NMR; T_(m) (by DSC)=122.2° C.).

Example 30 Ethylene polymerization with Nickel Catalyst Derived fromNi(acac)₂, B(C₆F₅)₃, Ph₃C(C₆F₅)₄ and Ligand v22

A 1 L Parr® autoclave, Model 4520, was dried by heating under vacuum to180° C. at 0.6 torr for 1 h, then cooled and refilled with dry nitrogen.The autoclave was charged with dry, deoxygenated hexane (450 mL) and 2.0mL of a 0.25 M solution of triisobutylaluminum in hexanes. The reactorwas sealed and heated to 80° C. under nitrogen, then sufficient hydrogenwas added to raise the pressure by 8.9 psi, after which sufficientethylene was introduced to raise the total pressure to 250 psig. Asample loop injector was first purged with 2.0 mL dry, deoxygenateddichloromethane (injected into the reactor), and then used to inject3×2.0 mL of a stock solution (corresponding to a toal of 3.0 μmol ofpro-catalyst) prepared from 17.34 mL of CH₂Cl₂ and 2.66 mL of a stocksolution prepared from 45.3 mg ligand v22, 15.0 mg Ni(acac)₂, 54 mgPh₃C(C₆F₅)₄ and a total of 19.546 g (14.75 mL) CH₂Cl₂, followed by 2.0mL of CH₂Cl₂, using ethylene gas to force the liquids into the autoclaveand raise the pressure to ca. 440 psig, after which time the reactor wasisolated and the pressure was allowed to fall to about 380 psig. Moreethylene was then reintroduced to raise the pressure back to ca. 440psig, and the cycle was repeated throughout the experiment to give anaverage pressure of 404 psig, and an average temperature was 80.4° C.After 52 min, the reaction was quenched by injection of MeOH, then thereactor was cooled, depressurized and opened. The polyethylene wasrecovered by concentrating the mixture to dryness under vacuum to obtain13.01 g amorphous polyethylene.

Example 31

The procedure of Example 30 was followed without change, except theaverage temperature was 60.1° C., the average pressure was 605 psig, thepartial pressure of hydrogen was 4.49 psi, and the total reaction timewas 59.7 min. This afforded 38.6 g amorphous polyethylene, correspondingto 460,000 mol ethylene/mol nickel.

Example 32 Preparation of a Compound of Formula kk1

Bis(thioamide) aaa14 is reacted with 1 equivalent of Bu₂Sn(OSO₂CF₃)₂ and2 equivalents of a non-nucleophilic base, such as2,4,6-tri-tert-butylpyridine to afford a compound of formula kk1, withM¹L_(n)=Bu₂Sn, andAr^(2a)=Ar^(2b)=2,6-di(4-tert-butylphenyl)-4-phenylphenyl.Alternatively, bis(thioamide) aaa14 is reacted with 1 equivalent ofCp₂Zr(NMe₂)₂ to afford a compound of formula kk1, with M¹L_(n)=Cp₂Zr,and Ar^(2a)=Ar^(2b)=2,6-di(4-tert-butylphenyl)-4-phenylphenyl.

Example 33 Preparation of a Compound of Formula kk2

2 equivalents of bis(thioamide) aaa14 are reacted with 1 equivalent ofSnCl₄ or TiCl₄ and 4 equivalents of a non-nucleophilic base, such as2,4,6-tri-tert-butylpyridine to afford a compound of formula kk2, withM¹L_(n)=Sn or Ti, andAr^(2a)=Ar^(2b)=2,6-di(4-tert-butylphenyl)-4-phenylphenyl.Alternatively, 2 equivalents of bis(thioamide) aaa14 are reacted with 1equivalent of Ti(NMe₂)₄ to afford a compound of formula kk2, withM¹L_(n)=Ti, andAr^(2a)=Ar^(2b)=2,6-di(4-tert-butylphenyl)-4-phenylphenyl.

We claim:
 1. A catalyst composition useful for the polymerization ofolefins, which comprises a Group 8-10 metal complex comprising abidentate or variable denticity ligand comprising two nitrogen donoratoms independently substituted by aromatic or heteroaromatic rings,wherein the ortho positions of said rings are substituted by aryl orheteroaryl groups.
 2. A catalyst composition useful for thepolymerization of ethylene, which comprises either (i) a compound offormula ee1, (ii) the reaction product of a metal complex of formula ff1and a second compound Y¹, or (iii) the reaction product ofNi(1,5-cyclooctadiene)₂, B(C₆F₅)₃, a ligand selected from the groupconsisting of Set 18, and optionally an olefin;

wherein: L² is a ligand selected from the group consisting of Set 18; Tis H, hydrocarbyl, substituted hydrocarbyl, or other group capable ofinserting an olefin; L is an olefin or a neutral donor group capable ofbeing displaced by an olefin; in addition, T and L may be bondedtogether to form a π-allyl or π-benzyl group; X⁻ is BF₄ ⁻, B(C₆F₅)₄ ⁻,BPh₄ ⁻, or another weakly coordinating anion; Q and W¹ are eachindependently fluoro, chloro, bromo or iodo, hydrocarbyl, substitutedhydrocarbyl, heteroatom attached hydrocarbyl, heteroatom attachedsubstituted hydrocarbyl, or collectively sulfate, or may be bondedtogether to form a π-allyl, π-benzyl, or acac group; Y¹ is either (i) ametal hydrocarbyl capable of abstracting acac from ff1 in exchange foreither alkyl or another group capable of inserting an olefin, (ii) aneutral Lewis acid capable of abstracting Q⁻ or W¹⁻from ff1 to form aweakly coordinating anion, a cationic Lewis acid whose counterion is aweakly coordinating anion, or a Bronsted acid whose conjugate base is aweakly coordinating anion, or (iii) a Lewis acid capable of reactingwith a π-allyl or π-benzyl group, or a substituent thereon, in ff1 toinitiate olefin polymerization; R^(3a,b) are each independently H,alkyl, hydrocarbyl, substituted hydrocarbyl, 2,4,6-triphenylphenyl,heteroatom connected hydrocarbyl, heteroatom connected substitutedhydrocarbyl, or fluoroalkyl; and Ar^(1a-d) are each independentlyphenyl, 4-alkylphenyl, 4-tert-butylphenyl, 4-trifluoromethylphenyl,4-hydroxyphenyl, 4-(heteroatom attached hydrocarbyl)-phenyl,4-(heteroatom attached substituted hydrocarbyl)-phenyl, or 1-naphthyl.3. The composition according to claim 2, wherein the metal complex offormula ff1 is selected from the group consisting of Set 19;

wherein: R^(3a,b) are each independently H, methyl, phenyl,4-methoxyphenyl, or 4-tert-butylphenyl; Ar^(1a-d) are each independentlyphenyl, 4-methylphenyl, 4-tert-butylphenyl, 4-trifluoromethylphenyl, or1-naphthyl; and X⁻ is BF₄ ⁻, B(C₆F₅)₄ ⁻, BPh₄ ⁻, or another weaklycoordinating anion.
 4. The composition according to claim 2, furthercomprising a solid support.
 5. The composition according to claim 3,wherein Ar^(1a-d) are 4-tert-butylphenyl or 1-naphthyl.
 6. A process forthe polymerization of olefins, comprising contacting one or more olefinswith the catalyst composition of claim
 2. 7. The process according toclaim 6, wherein the second compound Y¹ is trimethylaluminum, and saidmetal complex is contacted with the trimethylaluminum in a gas phaseolefin polymerization reactor.
 8. A catalyst composition comprising aGroup 8-10 transition metal complex which comprises a ligand selectedfrom group consisting of the formula kk1 and kk2;

wherein: Ar^(2a,b) are each independently aromatic or heteroaromaticgroups wherein the ortho positions are substituted by aryl or heteroarylgroups; M¹ is a metal selected from the group consisting of Groups 3, 4,5, 6, 13, and 14, or is Cu, P or As when the ligand is of formula kk1and M¹ is a metal selected from the group consisting of Groups 3, 4, 5,6, 13, and 14 when the ligand is of formula kk2; and L_(n) are ancillaryligands or groups which satisfy the valency of M¹, such that M¹ iseither a neutral, monoanionic or cationic metal center, with suitablecounterions such that said catalyst composition has no net charge.
 9. Aprocess for the polymerization of olefins, comprising contacting one ormore olefins with the catalyst composition of claim 8.